Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
  • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
  • C07D495/04—Ortho-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
  • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
  • C07D239/72—Quinazolines; Hydrogenated quinazolines
  • C07D239/95—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in positions 2 and 4

Definitions

• the present invention relates to of formula I, which have microbicidal activity, in particular fungicidal activity.
• the invention also relates to the preparation of these substances, to agrochemical compositions which comprise at least one of the novel compounds as active ingredient, to the preparation of the compositions mentioned and to the use of the active ingredients or compositions in agriculture and horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.
• A designates a fused benzene or thiophene fused in [2,3-d] position
• R-i is hydrogen or halogen
• R 2 is hydrogen or halogen
• R 3 is C 2 -C 5 alkyl or cyclopropylmethyl
• R 4 is C 2 -C 5 alkyl or cyclopropylmethyl, in the free form or in salt form.
• the bridge A designates a fused benzene or thiophene ring
• the fused aromatic ring system designates of the following substructures: - 2
• the compounds of formula I may be obtained in the form of their acid addition salts.
• Such acid addition salts are, for example, formed with mineral acids, typically sulfuric acid, a phosphoric acid or a hydrogen halide, with organic carboxylic acids, typically acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, with hydroxycarboxylic acids, typically ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or with benzoic acid, or with organic sulfonic acids, typically methanesulfonic acid or p-toluenesulfonic acid.
• the invention relates to the pure isomers, such as enantiomers and diastereomers, as well as to all possible mixtures of isomers, e.g. mixtures of diastereomers, racemates or mixtures of racemates.
• alkyl denotes ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, tert-pentyl, and neo-pentyl.
• Non- branched alkyl is preferred.
• Halogen will be understood generally as meaning fluoro, chloro, bromo or iodo. Fluoro, chloro or bromo are preferred meanings.
• Ri is halogen, preferably chlorine or bromine
• R 2 is hydrogen
• R 3 is C -C 4 alkyl, preferably propyl or butyl
• R is C 2 -C alkyl, preferably propyl or butyl.
• 6-chloro-2-propoxy-3-propyl-4-thioxo-thieno[2,3-d]pyrimidine 3-butyl-6-chloro-2-propoxy-4-thioxo-thieno[2,3-d]pyrimidine, 6-bromo-2-propoxy-3-propyl-4-thioxo-thieno[2,3-d]pyrimidine, and 6-bromo-3-butyl-2-propoxy-4-thioxo-thieno[2,3-d]pyrimidine.
• the compounds of formula I may be obtained by treatment of a compound of formula II
• A, R**, R 2 , R 3 and R 4 are as defined for formula I, with a sulfurating agent, e.g. P S 5 or the Lawesson reagent.
• a sulfurating agent e.g. P S 5 or the Lawesson reagent.
• the reaction conditions for sulfurating reactions of this type are well known in the art (B.A. Jones, J.S. Bradstaw, Chem. Rev. 1984 (84), 17-30) and for the purpose of present invention is conveniently carried out in analogy to known procedures.
• the reaction is carried out in an inert solvent, e.g. dioxane, tetrahydrofurane, toluene, xylene and the like, and at a temperature in the range of the boiling point of the reaction mixture, conveniently at reflux.
• the starting material of formula II is known from the prior documents cited above.
• the compounds of formula I may be obtained by alcoholysis of a compound of formula HI
• the base is selected from the alkali salts of the employed alcohol, and the reaction is carried out in a excess of the alcohol which may at the same time serve as solvent.
• the alcohol may be employed only in slight excess, and an inert solvent may be employed.
• NXS N-Hal-succinimide - 6 -
• novel compounds of formula I have, for practical purposes, a very advantageous spectrum of activities for protecting plants against diseases that are caused by fungi as well as by bacteria and viruses.
• the compounds of formula I can be used in the agricultural sector and related fields of use as active ingredients for controlling plant pests.
• the novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous cultivated plants.
• the compounds of formula I can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.
• compounds of formula I as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
• the compounds I are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemiieia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Ven- turia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara).
• Fungi imperfecti e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria
• Basidiomycetes e.g. Rhizoctonia, Hemiieia, Puccinia
• novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).
• target crops to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinache, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as
• the compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances.
• the methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
• the compositions may also contain further adjuvants such as stabilisers, antifoams, viscosity regulators, binders or tackifiers as well as fertilisers, micronutrient donors or other formulations for obtaining special effects.
• Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers. Such carriers are for example described in WO 97/33890.
• the compounds of formula I are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds.
• further compounds can be e.g. fertilisers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
• the 4-thioxopyrimidines of formula I in general exhibit a relative lower vapor pressure than the analogous 4-pyrimidinones.
• the compounds of formula 1 surprisingly show improved antifungal activity in leaf treatment application in climate zones with relatively warm average - 8 -
• the compounds of formula I provide improved biological performance properties for the agricultural practice by requiring less frequent repetition of the application, and at the same time providing equal or improved level of protection.
• the compounds of formula I can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities.
• azoles such as azaconazole, bitertanol, propiconazole, difenoconazole, diniconazole, cyproconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, tebuconazole, tetraconazole, fenbuconazoie, metconazole, myclobutanil, perfurazoate, penconazole, bromuconazole, pyrifenox, prochloraz, triadimefon, triadimenol, triflumizole or triticonazole; pyrimidinyl , carbinoles such as ancymidol, fenarimol or nuarimol; 2-amino- pyrimidine such as bupirimate, dimethirimol or
• fluazinam flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, kasugamycin, methasulfocarb, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine or validamycin.
• a preferred method of applying a compound of formula I, or an agrochemical composition which contains at least one of said compounds, is foliar application.
• the frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen.
• the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field.
• the compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
• compositions containing the compound of formula I and, if desired, a solid or liquid adjuvant are prepared in known manner, typically by intimately mixing and/or grinding the compound with extenders, e.g. solvents, solid carriers and, optionally, surface active compounds (surfactants).
• extenders e.g. solvents, solid carriers and, optionally, surface active compounds (surfactants).
• the agrochemical formulations will usually contain from 0.1 to 99 % by weight, preferably from 0.1 to 95 % by weight, of the compound of formula I, 99.9 to 1 % by weight, preferably 99.8 to 5 % by weight, of a solid or liquid adjuvant, and from 0 to 25 % by weight, preferably from 0.1 to 25 % by weight, of a surfactant.
• Advantageous rates of application are normally from 5 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, most preferably from 20 g to 600 g a.i./ha.
• convenient dosages are from 10 mg to 1 g of active substance per kg of seeds.
• Barley plants about 8 cm in height are drenched with an aqueous spray mixture
• Example B-2 Action against Podosphaera leucotncha on apple shoots
• Apple cuttings with fresh shoots about 15cm long are sprayed with a spray mixture
• the plants are infected 24 hours later with a conidia suspension of the fungus and stood in a climatic chamber at 70% relative humidity and 20°C. Evaluation of the fugal infestation is made 12 days after infection.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=10826428

Family Applications (1)

Country Status (7)

Families Citing this family (7)

Family Cites Families (4)

• 1998
  • 1998-02-04 GB GBGB9802355.9A patent/GB9802355D0/en not_active Ceased
• 1999
  • 1999-02-02 AU AU29242/99A patent/AU2924299A/en not_active Abandoned
  • 1999-02-02 WO PCT/EP1999/000686 patent/WO1999040074A1/en not_active Application Discontinuation
  • 1999-02-02 BR BR9909738-9A patent/BR9909738A/pt not_active IP Right Cessation
  • 1999-02-02 US US09/601,662 patent/US6384040B1/en not_active Expired - Fee Related
  • 1999-02-02 JP JP2000530504A patent/JP2002502846A/ja active Pending
  • 1999-02-02 EP EP99910184A patent/EP1053229A1/en not_active Withdrawn

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events